Purification of valuable hydro-



Patented Jan. 1 4, 1941 v o 2,228,788 PURIFICATION or VALUABLE immocannons V Frank J. Soday, Upper Darby, Pa., assignor to The UnitedGasImprovement Company, a corporation of Pennsylvania No Drawing. Application May 27, 1938 Serial No. 210,423

5 Claims. (oi. zoo-cs9) The invention pertains more particularly to the purification of crude fractions of resin-forming unsaturatedhydrocarbons derived from light oil such as crude styrene, and crude methyljstyrenes.

In the various processes'for the manufacture of artificial gas suchas oil gas, carburetted water gas, or coal gas, considerablequantities of tar are pro duced, and the gas contains substantial quantities of other readilymondensible materials.

The latter condensates as well as the, distillate from thetar are known generally as light oil and are sources for many resin-forming unsaturated hydrocarbons such as styrene-and methyl styrene.

With ordinary methods of fractional distillation as now practiced, it isimpossible' to separate the resin-forming unsaturated hydrocarbons in a substantially pure state, because of the presence of other materials which apparently are either of similar boilingpoint or are capable of forming azeotropic mixturesfwith the desired hydrocarbon. Furthermore, manyof these materials are polymerizable with heat which adds to distillation difllculties.

Forinstance a typical styrene fraction obtained by ordinary distillation processes will contain hardly more than 50% styrene.

.Such fractions as well as those of lower and higher concentration are generally suitable for the manufacture of synthetic resins by polymerization, except that the resulting resins are very often too inferior with respect to color; color stability, electrical resistance, molding properties, freedom from crazing, thermal stability, melting point, specific viscosity, molecular weight and mechanical strength as to be of any considerable value. i a

I find that these deficiencies are generally traceable to the presence during the polymerization of certain contaminating materials. o

While I have not as yet exactly determined the character of these impurities, experimental evidence indicates that they may be classified in color from a faint yellow to a light-brown. This indicates, among other things, the presence of superaromatic compounds such as substitute thiophene and thiophene homologues.

The treatment of various light oil fractions 5 with ammoniacal cuprous chloride resulted in the formation of a heavy yellow precipitate. This indicates the presence of acetylenic compounds such as phenyl acetylene.

Similar tests made with pure styrene diluted 10 with xylene to the same concentration as the crude styrene fractionstreatedabove gave results which were negative in each' case.

Other types of impurities are doubtlessypresent also, although specific tests have not asyet been devisedfor their detection. Among these types of impurities .may be included oxygenated compounds, organic peroxides and oxides, organic per acids, aldehydes, amines, and other reactive classes of compounds. I v20 As indicated above it is difllcult, if not impossible, to prepare a commercial grade of resin, such as polystyrene, from crude light oil fractions unless at least some of the contaminating impurities are removed. l 25 While the exact influence of these contaminating materials is not known it may be pointed out that they may act (1) as accelerators resultingin the production of polystyrene of relatively poor quality under polymerizing conditions which would; 130

normally result in the production of a good'grade' 3 of polystyrene;v (2)- as inhibitors reducing the quantity of polystyrene obtained under. normal polymerizing conditions; and/or (3) they may take part in the reaction and become an integral part of the resin molecule.

The presence of contaminating impurities in the polymer molecule would undoubtedly weaken it, causing the resin to be less stable to heat and to readily decompose with the formation. of un desired color bodies. k v v The highly reactive nature of the'resin-forming unsaturated hydrocarbons makes it extremely difficult to remove the contaminating impurities. For instance, customary methods for the removal of impurities, such as sulfur compounds, diolefines and acetylenes, from cracked distillates in the manufacture of motor fuels removes'most, if 'not all, of any styrene present. I V o v I It seems probable that any material which is sufficiently reactive to be capable of use, for the purification of the crude resin-formingunsaturated hydrocarbonswill react with them.

Technologists have made many attempts to utilize sulfuric acid for refining light oil distillates. Such attempts have been unsuccessful, since the treatment invariably caused the removal of the greater portion of the unsaturated compounds present.

I have-found, however, that, by a proper choice of conditions such as temperature, time of contact, method of application and so forth, the various reactions may be controlled with the result that practically all of the undesired contaminating materials, including color and color-forming compounds, may be removed without a considerable loss of the desiredhydrocarbon.

The following examples will serve to illustrate the invention:

' Example 1 A 500 cubic centimeter (444 grams) sample of a typical crude styrene cut obtained from the fractionation of light oil and containing 33.3 grams of styrene per 100 cubic centimeters was agitated for 5 minutes with 2.5 cubic centimeters of 100% sulfuric acid at a temperature of -20 C. The mixture was then allowed to stand for 4 minutes during which time a sludge settled out and was removed.

An additional 2.5 cubic centimeters of the foregoing reagent was then added and the mixture again agitated for 5 minutes. A settling time of 4 minutes followed after which sludge was removed.

A 5 gram portion of fullers earth was added. This was followed by agitation for a few minutes whereupon the fullers earth was removed by filtration.

The sample was. then treated with 10 cubic centimeters of a 20% aqueous solution of sodium hydroxide with vigorous stirring. After permitting the materials to settle the aqueous layer was removed.

The sample was now washed successively with water until the last washings were neutral to litmus which indicated complete removal of acid and alkaline residues.

The total treating loss up to this point was 16.8% by weight of the starting material.

The refined sample of crude styrene was now dried over anhydrous sodium sulfate.

The drying loss was 5.5% by weight of the starting material. Although this loss is not excessive, I wish to point out that it was due almost entirely to mechanical absorption by the drying agent and that the lost material might be reclaimed by washing the anhydrous sodium sulfate with a suitable solvent.

The dried material was then distilled under vacuum using a pressure of 40 millimeters absolute.

This occasioned an additional loss of 3.9% by weight of theoriginal charge.

The crude styrene wasnow ready for polymerization.

It is to be noted that despite the reactive nature of the reagent and of the material being treated the total treating loss was only 26.2% by weight of the starting material. A considerable part of these losses were of a mechanical nature and are, therefore, susceptible to considerable reduction, particularly in large scale operations.

The refined styrene solution had a color on the well known Gardner color scale of 0.5 as compared to a color of 2.5 shown by the starting material.

The refined material gave a negative reaction with mercurous chloride solution, indicatingcomplete removal of the hydroaromatic compounds.

Sulfur analysis indicated that of the sulfur compounds originally present were removed.

A sample of the refined styrene solution was subjected to polymerization for 4 days at a temperature of 145 C. in a nitrogen atmosphere.

The resin yield was 27.4 grams per cubic centimeters of refined solution. The starting material itself contained 33.3 grams of styrene per 100 cubic centimeters of crude solution. The styrenerecovery was 60.7% of the styrene in the original charge.

Another sample of the refined styrene solution and a sample of the starting material were each subjected to identical polymerizing conditions, namely heating for a 10 day period at 100 C. in an atmosphere of nitrogen.

The resin obtained from the refined material had a. color of 1.0 on the Gardner color scale, whereas the resin obtained from the unrefined material had a color of 2.0 on the Gardner color scale.

Furthermore, the refined resin possesses unusual color stability as shown by the following test.

A sample of resin obtained from the refined material and a sample of resin obtained from the unrefined material were each heated for 2 days in an atmosphere of nitrogen and an atmosphere of air at a temperature of C.

At the end of this rather severe treatment the refined resin had a color of 7.5 and 8.0 respectively on the Gardner color scale, whereas the unrefined resin had a color of 12.0 and 12.5 respectively on the Gardner color scale.

The melting point of the refined resin was 0., whereas the melting point of the unrefined resin was 154 C.

Tests also show that the refined resin possesses a much better mechanical strength and is tougher than the unrefined resin, that its molding properties are considerably improved and that it is more uniform in texture and appearance.

Example 2 A 500 cubic centimeter (437.6 grams) sample of a typical crude styrene cut obtained from the fractionation of light oil and containing 33.3 grams of styrene per 100 cubic centimeters was agitated for 10 minutes with 10 cubic centimeters of 70% sulfuric acid at a temperature of 20 C. The mixture was then allowed tostand for 32 minutes during which time a sludge settled out and was removed.

The above procedure was repeated four times, that is until a total of 50 cubic centimeters of acid was used up.

The sample was then treated with 25 cubic centimeters of a 20% aqueous solution of sodium hydroxide with vigorous stirring. After permitting the materials to settle the aqueous layer was removed.

The sample was now washed successively with water until the last washings were neutral to litmus which indicated complete removal'of acid and alkaline residues.

The total treating loss up to this point was 0.3% by weight of the starting material.

The refined sample of crude styrene was now dried over anhydrous sodium sulfate.

The drying loss was 32% by weight of the starting material. Although this loss is not excessive,

I wish to point out that it was due almost entirely to mechanical absorption by the drying agent and that the lost material might be reclaimed by washing the anhydrous sodium sulfate with a suitable solvent.

lute.

This occasioned an additionalloss of 3.0% by weight of the original charge. The crude styrene was now ready for polymeri- It is to be noted that despite the reactive nature of thereagent and of the material being treated the total treating losswas only 7.4% by weight of the starting material. Most of these losseswere of a mechanical natureand are; therefore, susceptible to considerable reduction, particularly in large scale operations.

The refined styrene solution had a color on the well known Gardner color scale of f 0.0 (water white), as compared toa, color of 2.5 shown by the starting material.

The refined material gave a negative reaction with mercurous chloride solution, indicating complete removal of the hydroaromatic compounds.

Sulfur analysis indicated that 40% of sulfur compounds: originally present were removed.

A sample of the refined styrene solution was subjected tr. polymerization for 4 days at atemperature of 145 C. in a nitrogen atmosphere.

The resin yield was 31.5-gramsper'100 cubic centimeters of refined solution. The starting material itself contained 33.3 grams of styrene per 100 cubic centimeters of :crude solution. The styrene recovery was 83.9% of the styrene in the original charge. 1

Another sample of the refined styrene solution and a sample of the starting material were each subjected to identical polymerizing conditions, namely heating for a 10 day period at 100 C. in an atmosphere of nitrogen. V

The resin obtained from the refined material had a color of 1.0 on the Gardner color scale, whereas the resin obtained from the unrefined material had a color of 2.0 on the Gardner color scale.

A sample of each portion of resin was subjected to moldmlg at a temperaturezof 200? .C. and a a muchbetter mechanic 7 than the unrefined resin, that its molding proppressure of 2000 pounds per square-inch. The

molded reaned material had a colorio f 1.2 on the f Gardner color scale, whereas the molded unrefined material had a color of 2.4 on the Gardner color scale.

Furthermore, the refined .resin possesses unusual color stability as shown by the following test. 'A sample of resin obtained from the refined material and a sample of resin obtained from the unrefined material were each heated for .2 days in an atmosphere of nitrogen and an atmosphere of air at a temperature'of 145 C.

At the end of this rather severe treatment the refined resin had a color of 6.5 and 8.5respectively on the Gardner colorscale, whereas the unrefined resin had a color of 12.0 and 12.5 respectively on the Gardner color scale.

The melting point of the refinedresin was 174 0., whereas the melting point of the unrefined resin was 154 C.

Tests also'show that the refined resin possesses al strength and is tougher erties are considerably improved and that it is more uniform in texture and appearance.

Example 3 A 500 cubic centimeter (443.2 grams) of a typical crude styrene cut obtained-from the fractionation of light oil and containing 49.7 grams of styrene per 100 cubic centimeters was agitatedfor 10 minutes with cubiccentimeters of 65% sulfuric The sample was then treated with 25 cubic cen-' timeters of a 20% aqueous solution of sodium hydroxide with vigorousstirring. After permitting the materials to settle the aqueous layer was removed. i

Thesample was now washed successively with Water until; the last washings were neutral to litmus which indicatedcomplete removal of acid and alkaline residues. v t

The total treating loss up to this point by weightof the starting material. V, l

The refined sample of crude. styrene was now driedover'anhydrous sodium sulfate. h

The drying loss was 1.7% by weight of the starting material.

was 0.3%

out that it was due almost entirely to mechanical that the lost material might be reclaimed by washing the anhydrous sodium sulfate wifha suitable solvent.

of the reagent "and of the total treating loss the starting material.

of amechanical nature and are, therefore, susceptible to considerable reduction, particularly in large scale operations.

The refined styrene solution had a color on thewell' known Gardner color scale of 0.1 as compared to a, color of 2.5 shown by the starting material.

The refined material with mercurous chloride solution, indicating completeremoval of the hydroaromatic compounds. Sulfur analysis indicated that of the sulfur compounds originally present wereremoved.

Asample of the refined styrene solution was subjected to polymerization for 4 days at a temperature of 145 C. in a nitrogen atmosphere The resin yield was'50.2 grams per 100 cubic centimeters of refined solution. The starting material itself contained 49.7 grams of styrene per 100" cubic centimeters of crude solution. The styrene recoverywas 96.6% of the styrene in the original charge.

Another sample of the and a sample of the starting material were each subjected to identical polymerizing conditions, namely heating foria 10 day period at 100 C. in an atmosphere of nitrogen.

Although this loss is not excessive, :25 absorption by the drying agent and gave a negative reaction refined styrene solution The resin obtained from the refined material had a color of 0.5 on the Gardner color scale, whereas the resin obtained from the unrefined material had a color of 1.0 on the Gardner color scale.

A sample of each portion of resin was sub-. jected to molding at a temperature of 200 C. and a pressure of 2000 pounds per square inch. The molded refined material had a colorof 0.3

on the Gardner color scale, whereas the molded unrefined material had a color of 2.4 on the Gardner color scale. I v

The melting point of the refined resin was 187 0., whereas the melting point of the unrefined.

resin was 169 C. V

Tests. also .show that the refined resin possesses a much better mechanical strength and is tougher than the unrefined resin, that itsv molding properties are considerably improved and that it is more uniform intexture and appearance.

Example 4 d v 1 A500 cubic centimeter (443.9 grams) of'a typical crude styrene cut obtained from the fractionation of light oil and containing 66.2 grams of styrene 'per 100 cubic centimeters was agitated for 10 minutes with 25 cubic centimeters of 50% water until treated with 25 cubic centimeters of a 20% aqueous solution of sodium hydroxide withstirring; After permitting the materialsto settle the aqueous layer was removed. The sample was now washed successively with the .last washings were neutral to litmus which indicated complete removal of acid and alkaline residues. 275 cubic centimeters of water was used.

The refined sample of crudastyrenewas now 5 dried over anhydrous sodium sulfate for several material might ,loss is not excessive,

'treatedthe total treatingloss was ticularly in large scale hours. The totalloss up to this point was 2.7% by weight of the starting material. Although this I wish to point out that it was almost entirely mechanical and that thelost be reclaimed. I The dried material was then distilled under vacuum using a pressure of 40 millimeters absolute;

This occasioned an additional loss of 0.7% by weight' of the original charge.

. The crude styrene was now ready for polymerization.

It is to be ture of the reagent and of the noted that despite the reactive namaterial being only 3.4%. by weight of the starting material. Most ofthese losses were of a fore, susceptible to considerable reduction, paroperations. The refined styrene solution had a color on the well known Gardner color scale of 1.9 as compared to a. color of 2.5 shown by the starting material. j v

The refined material gave a very faint reaction with 'mercurous chloridesolution and with ammoniacal cuprous chloride solution indicating almost complete removal of the superaromatic and acetylenic compounds. Sulfur analysis indicatedthat 95% of the sulfur compounds originally present were removed. A sample of the refined styrene solution was subjected to polymerization for 4 days at a temperature of 145"; C. in a nitrogen atmosphere.

The resin yield was.66.4 grams. per 100 cubic centimeters of refined solution. The startin material itselfcontained 66.2 grams of. styrene per lfcubic centimeters of crude solution. The

A settling time mechanical nature and are, there styrene recovery was apparently 100% of the styrene in the original charge. Treating losses were, therefore, solely at the expense of undesired constituents.

Another sample of the refined styrene solution and a sample of the starting material were each subjected to identical polymerizing conditions, namely heating for a 10 day period at 100 C. in an atmosphere of'nitro'gen.

The resin obtained from the refined material had a color of 0.5 on the Gardner color scale, whereas the resin obtained from the unrefined material had a color of 0.8 'on the Gardner color scale. 1

.. Example 5 A 500 cubic centimeter (447.3 grams) sample of a typical crude styrene cut obtained from the fractionation of light oil and containing 66.2 grams of styrene per 100 cubic centimeters was agitated for minutes with 25 cubic centimeters of 60% sulfuric acid at a temperature of 20 C. ,The mixture was then allowed to standfor-32 minutes during which time a sludge settled out and was removed.

An additional 25 cubic centimeters of the foregoing reagent was then added and the mixture again agitated for 10 minutes. A settling time of 32 minutes followed after which sludge was removed.

The sample was then treated with 25 cubic centimeters of a 20% aqueous'solution of sodium hydroxide with stirring. After permitting the materials to settle the aqueous layer was removed.

The sample was now washed successively with water until the last washings were neutral to litmus which indicated complete removal of acid and alkaline residues. 250 cubic centimeters of waterwas used. v v The refined sample of crude styrene was now dried over anhydrous sodium sulfate.

The combined loss, up to this point, was 3.4% by weight of the starting material. Although this loss is not excessive, I wish to point out that it was almost entirely mechanical and that the lost material might be reclaimed.

The dried material was then distilled under {'atcuum using a pressure of 40 millimeters abso- This occasioned an additional loss of 1.1%,by weight of the original charge.

The crude styrene was now'ready for polymerization.

It is to be noted. that despite the reactive nature of the reagent and of the material being treated the total treating loss was only 4.5% by weight of the starting material. Most of these losses were of a mechanical nature and are,

"therefore, susceptible to considerable reduction,

particularly in large scale operations.

The refined styrene solution had a'color on the ,well known Gardner color scale of 1.5 as compared to a color of 2.5 shown by the starting material.

The refinedpmaterial gave a very faint reaction with mercurous chloride solution and with. ammoniacalcuprous chloride solution, indicating almost complete removal of superaromatic and acetylenic compounds. Sulfur analysis indicated that of sulfur compounds originally present were removed.

A sample of the refined styrene solution was subjected to polymerization for! days at a temperature of 145 C. in a nitrogen atmosphere.

The resin yield was 67.3 grams per cubic 751 centimeters of refined solution.- The starting material itself contained 66.2 grams of styrene per 100 cubic centimeters of crude solution. The styrene recovery was thus apparently 100% of the styrene in the originalcharge. The losses, therefore, were at theexpense of undesired constituents.v l i Another'sampleof the refined styrene solution and a sample of the starting material were each subjected to identical polymerizing conditions, namely heating for a 10 day period at 100 C. in an atmosphere of nitrogen. j if .The resin obtained from the refined material had a color of 0.6 on the Gardner color scale. whereas the resin obtained from the unrefined material hada color of 0.8 on. the Gardner color scale. I j

In the above examples various concentrations of styrene and various concentrations of sulfuric acid were used toillustrate differences in results due to such variations. What has been shownin this respect with sty-r rene applies comparably to methyl styrene.

While solutions of sulfuric acid of any desired 1 strength maybe employed, I prefer touse sulfuric acid of at least 50%;strength,fand up to say strength. Acid of higher or lower strength may be employed. For instance, acid of lower strength may be used for purifying solutions of oleflnes and diolefines of higher concentration. Acidof higher strength is preferably free of uncombined sulfur dioxide or sulfur trioxide.

I find that solutions of sulfuric acid of 60% to 80% concentration areverysatisfactory, and that a solution of 70% concentration is excellent for all around purposes. a

High concentrations lend themselves to conditions requiringmore drastic treatment. .1

Although any suitable proportion of acid may be employed,I prefer to use from, 0.2% to 50% by volume based upon-the material being treated.

I find that from 2% to 10%. of acid by volume of the materialundertreatment gives very satisfactory results. 1 -1 1 If desired suitableother-additions maybe made to the acidsolution. s M 1 Examples 01' materialswhich might be added to the acidysolution are (1) .-retarding agents, which have for theirspeciflc purpose the reduction of the effect of the acid upon the styrene and methyl styrene present in the fraction, 'such as boric acid and other compounds of boron as described and claimed in mycopending application Serial Number 210,745 filed May 28, 1938; (2) reducing agents, the functionof which is to remove highly, reactive impurities by means of, nascent hydrogen, such as zinc dust, iron iilings, aluminum powder, magnesium powder, tin dust, nickel powder and cadmium powder; and (3) inhibitors, the function of which is to inhibit the polymerization of theunsaturated hydrocarbons during the treating process, such as p-tertiarybutyl catechol, 2-4 diaininophenol,dihydrochloride, 2-amino-5 hydroxytolucne, p-benzyl aminophenol, and pyrogallol. l

Anycombination of 1), (2mm (3) ma be added lf,deslred. i

Acid mixtures may be useddwith excellentfresults. Examples of acids which may be ,mixed with the sulfuric ,acid; are acids or acid. anhydrides containing phosphorus such asthe phosphoric acids, the phosphorous acids, P205 andv P203, acetic acid, and sulfonic acids. Temperaturesbetween approximately 10 C. and 30 C. are generally satisfactory, except when an emulsion ,1

%acid is employed when temperatures of at least as low as *20 C. are recommended. In other words, the temperature; should decrease with increase in acid concentration toavoid any considerable permanent discoloration of the hydrocarbon due to the strength of the, acid. Permanent discoloration shows up after neutralization and washing with water, since neutralization and water washing remove a-temporary discoloration of the hydrocarbon due to treatment. on

the other hand, the temperature should not be so low as to stop the action of the acid. Active acid generally speaking becomes discolored.

Unless certain precautions are observed, the addition, of theneutralizing agent to the acid washed material may result in the formation of I, therefore, prefer to add the neutralizing solution slowly and with moderate agitation, although alternate procedures may be employed.

1 Such ialternate procedures; include (a) the re-.

trical precipitation, the, addition of various inorganic salts to the emulsion, and the like.

Any, other suitable neutralizing agent maybe employed for the removarof excess acid and acid.

residues from the material under treatment. Examples of such neutralizing agents are lime. NazCOa, KOH, ammonia, full'ers earth, clay and activated carbon. g a

These neutralizing agents may be applied in the solid form, or in the-form of solutions in water or-other solvent. 'I'hey-may be used alone, or in combination with one or more other neutralizing agents, in which case they may be added to the treated solution together, or successively. For ex ample, the acid-treated solution can be treated withclay to remove the major portion of the acid and sludge, present, the clay and adsorbed materials removed by filtration or by other suitable means, and solid NazcOa added to the solution to removeany residual acid or sludge present. Incidentally, this treatment usually serves to completely remove all of the water present in the treated solution, rendering unnecessary any further drying operations.

If desired, inert solvents such as petroleum naphtha and carbon tetrachloride may be added to the material under treatment either before or during the treating process.

Such materials are usually added to reduce the loss of styrene and -methyl styrene present, although they may have other functions.

Th'ecrude fractions whichmay be treated by my process may have any reasonable boiling range. a y For instance, crude styrene fractions may have a boiling range of from C. to 165 C. or wider, although I prefer to use crudestyrene fractions, with boiling'rangeswhich do not greatly exceed C. to C.

Excellent results are obtained when using crude styrene fractions with boiling. ranges not exceeding 142 C. to 148C.

What has just been said with respect to the boiling ranges of crude styrene fractions applies comparably to fractions of methyl styrene.

For instance, a valuable methyl styrene fraction composed largely of para-methyl and metamethyl styrenes is obtained from light oil when at least approximately 80% boils between 167 C. and 175 C.

In general, and with all other conditions unchanged, the extent" of purification will, generally speaking, be directly proportional to the narrowness in boiling range of the starting material.

Results comparable to those particularly set forth above in connection with styrene are obtained upon the polymerization of methyl styrene treated by my process.

As an example a purified methyl styrene fraction may be polymerized by subjecting it to a temperature of 80 C. for a period of 8 days, followed by removal of unpolymerized material by vacuum distillation. The polymerized material has a color of 0.0 (water white) on the Gardner color scale.

A crude styrene solution containing any quantity of styrene such as from 1.0% to 99% may be refined by my method.

Excellent results are obtained with styrene solu tions containing from 10% to 80% styrene.

Comparable concentrations apply to methyl styrene refined by my method.

Contact between the material undergoing treatment and the treating material, namely acid, alkali (or other neutralizing agent), or water may be accomplished by any means known in the art.

For instance, any suitable batch, multiple batch, batch countercurrent, continuous countercurrent, or continuous concurrent contacting apparatus and method may be employed.

In this respect reference is had particularly to the large number of processes and apparatus for leaching generally, for bringing mineral, oil into contact with a chemical reagent, for the solvent extraction of mineral oils, etc., which may be adapted for carrying out the invention.

In certain cases it may be advisable to treat the unsaturated hydrocarbon, or fractions containing the unsaturated hydrocarbon, with successive portions of the acid solution in order to effect a more thorough purification of the hydrocarbon solution, or a more economical utilization of the acid mixture, or both. The batchwise addition of the acid mixture may be made with or without the removal of a portion or all of the acid and acid sludge from the preceding application and with or without additional refining steps, such as neutralization, drying, fractionation, and/or crystallization between successive batchwise additions of the acid refining agent.

' ing, fractionation and/or distillation, and the refining operation completed in the-normal manner, namely by separation of the respective layers, followed by neutralizing, drying, and/or distilling.

The treated material, of course, lends itself to further purification, should this be desired. Such further purification may be by contact with clay, with activated carbon, or with diatomaceous earth at any suitable temperature, or by distillation'at any desired pressure, orby partial polymerization followed by removal of undesirable constituents, or by fractional crystallization, or by other physical or chemical means.

Other variations will become apparent to persons skilled in the art upon becoming familiar with this invention.

The treating process as outlined in the example listed may be greatly simplified in most cases. For example, I find that styrene solutions may be refined in a satisfactory manner by treatment with the acid followed by the application of clay or activated carbon, either alone or in conjunction with other neutralizing agents, such as sodium carbonate or lime, and the removal of all solid material from the treated solution by filtration or by other suitable means. No further treatment is usually necessary.

The term permanent color as used in the claims is intended to mean color which remains after the removal of acid and acid reaction products such as by neutralization and water washing followed by distillation.

It is, therefore, to be understood that the above examples are by way of illustration and that changes, omissions, additions, substitutions, and/or modifications might be made within the scope of the claims without departing from the spirit of the invention which is intended to be limited only as required by the prior art.

I claim:

1. A process for the purification 'of the resinforming unsaturated hydrocarbon content of a light oil fraction selected from the group consisting of a light oil styrene fraction and a light oil methyl styrene fraction which comprises contacting said light oil fraction in the liquid phase with a reagent comprising'sulfuric acid at least 50% in concentration but free from any appreciable uncombined sulfur dioxide and sulfur trioxide, said contact of said fraction and said reagent'taking place at a temperature below 30 C. with the maximum temperature decreasing from 30 C. with-increase in concentration of said acid above 50% down to 20 C. when acid is used, said treating conditions being sufiiciently drastic to remove color forming bodies but insufilciently drastic to polymerize a large part of said resinforming unsaturated hydrocarbon content and insufllciently drastic to add any appreciable permanent color to said fraction, and removing said reagent from said fraction.

2. A process for preparing a refined out of a resin-forming unsaturated light oil hydrocarbon selected from a group consisting of styrene and methyl styrene which is highly resistant to color formation when subjected to conditions for the polymerization'of said unsaturated hydrocarbon which comprises subjecting light oil to fractional distillation to obtain a close out of one of a group consisting of styrene and methyl styrene, treating said out in the liquid phase with from 0.2% to 50% by volume of sulfuric acid free from any appreciable uncombined sulfur dioxide and sulfur trioxide, said acid being at least 50% in concentration, said treatment taking place at a temperature below 30 C. with the maximum temperature decreasing from 30 C. with increase in concentration of said acid above 50% down to 20 C. when 100% acid is used, said treating conditions being sufliciently drastic to remove color forming bodies but insufliciently drastic to polymerize a large part of said resin-forming unsaturated hydrocarbon and insufiiciently drastic. to add any appreciable permanent color to said out, and removing said reagent from said out.

3. In a. process for the purification of a resinforming unsaturated hydrocarbon :derived from light oil and selected from the group consisting of styrene and methyl styrene, the steps of treating said hydrocarbon in the liquid phase with sulfuric acid which is freefrom any appreciable uncombined sulfur dioxide and sulfur trioxide, said treatment taking place at a temperature below 30 C. with themaximum temperature decreasing from 30 C. with increase in concentration of said acid above 50% down to C. when 100% acid is used; said treating conditions being sufficiently drastic to remove color forming bodies but insufliciently drastic to polymerize a large part of said resin-forming unsaturated hydrocarbon and insufficiently drastic to add any appreciable permanent color to said hydrocarbon, and removing said reagent from said hydrocarbon.

4. A process for preparing a refined styrene out which comprises subjecting light oil to fractional distillation to obtain a cut the preponderate part of which boils between 142C. and 148 (2., treating said out with sulfuric acid which is free from any appreciable uncombined sulfur dioxide and sulfur trioxide, said acid being at least 50% in concentration, said treatment taking place at a temperature below C. with the maximum temperature decreasing from 30 C. with increase in concentration of said acid above down to 20 C. when acid is used, said treating conditions being sufliciently drastic to remove color forming bodies but insufliciently drastic to polymerize a large part of said styrene and insufiiciently drastic to add any appreciable permanent color to said cut, and removing residual acid from said styrene cut.

5. A process for preparing a refined methyl styrene cut which comprises subjecting light oil to fractional distillation to obtain a cut the preponderate part of which boils between 167 C.

and C., treating said out with sulfuric acid which is free from any appreciable uncombined sulfur dioxide and sulfur trioxide, said acidbeing at least 50% in concentration, said treatment taking place at a temperature below 30 C. with the maximum temperature decreasing from 30 C'. 

